Surface Raman spectroscopic investigation of pyridine adsorption at platinum electrodes - effects of potential and electrolyte

Surface enhanced Raman spectra of pyridine (Py) at Pt electrodes have been investigated as a function of potential and supporting electrolyte. The results show a large difference from those reported for coinage metal electrodes of Ag, Au and Cu, emphasising the effective involvement of chemical enhancement on Pt surfaces. At very negative (or positive) potentials, Raman spectra show the competitive coadsorption of hydrogen (or oxygen-containing species) with Py, and in acidic solutions, PyH+ ions prefer to dissociate into Py adsorbed on Pt surfaces even in the presence of chloride ions. The differences in the surface bonding strength for Py on Pt and coinage metal electrodes are explained in terms of the different electronic configurations of the metals.